海藻基CDs-Cu-TiO2复合材料的制备及其光催化性能

doi:10.15541/jim20210076

无机材料学报 ›› 2021, Vol. 36 ›› Issue (11): 1154-1162.DOI: 10.15541/jim20210076

所属专题：【能源环境】量子点

海藻基CDs-Cu-TiO₂复合材料的制备及其光催化性能

刘彩(), 刘芳, 黄方, 王晓娟()

中国石油大学(华东) 化学工程学院, 重质油国家重点实验室, 青岛 266580

收稿日期:2021-02-05 修回日期:2021-04-13 出版日期:2021-11-20 网络出版日期:2021-04-25
通讯作者: 王晓娟, 副教授. E-mail: xwang@upc.edu.cn
作者简介:刘彩(1996-), 女, 硕士研究生. E-mail: liucai662@163.com
基金资助:
青岛市科技惠民专项(17-3-3-76-nsh)

Preparation and Photocatalytic Properties of Alga-based CDs-Cu-TiO₂ Composite Material

LIU Cai(), LIU Fang, HUANG Fang, WANG Xiaojuan()

State Key Laboratory of Heavy Oil Processing, College of Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, China

Received:2021-02-05 Revised:2021-04-13 Published:2021-11-20 Online:2021-04-25
Contact: WANG Xiaojuan, associate professor. E-mail: xwang@upc.edu.cn
About author:LIU Cai(1996-), male, Master candidate. E-mail: liucai662@163.com
Supported by:
Qingdao Municipal People's Livelihood Science and Technology Project(17-3-3-76-nsh)

摘要/Abstract

摘要：

光催化降解技术能够高效去除废水中的有机污染物, 具有广阔的应用前景。本研究以海藻为碳源, 采用微波水热法制备海藻基碳量子点(CDs), 并进一步合成CDs-Cu-TiO₂复合材料作为可见光催化剂用于污染物降解。结果表明, 复合材料中CDs、Cu²⁺与TiO₂紧密结合在一起, 可见光区吸收明显增强, 荧光发射效率降低。CDs与Cu²⁺的引入产生协同效应, 使复合材料的禁带宽度降低到2.35 eV, 并有效抑制了电子-空穴的复合。以罗丹明B为污染物模型的光催化性能实验显示, 海藻基CDs-Cu-TiO₂复合材料在可见光照射下降解RhB的一级反应速率常数能够达到纯TiO₂纳米颗粒的6.4倍, 150 min降解率接近100%, 是TiO₂纳米颗粒的2倍。

关键词: CDs-Cu-TiO₂, 复合光催化剂, 光催化降解, 染料废水

Abstract:

Photocatalytic degradation can efficiently reduce the organic pollutants in wastewater which has broad application prospects. Herein, an algae Enteromorpha Prolifera, was used as the raw material to prepare alga-based carbon dots (CDs) through a hydrothermal method, and CDs-Cu-TiO₂ composite nanomaterials were further synthesized as a photocatalyst for pollutant degradation. The results show that CDs, Cu ²⁺ and TiO₂ are closely combined within the composite material. Compared to the pure TiO₂ nanoparticles, the absorption of CDs-Cu-TiO₂ in the visible light range is significantly enhanced and the fluorescence emission efficiency is decreased. Introduction of CDs and Cu²⁺produces a synergistic effect, which changes the band gap of the composite material to 2.35 eV, and effectively inhibits the recombination of electrons and holes. The photocatalytic degradation experiment using Rhodamine B as a model pollutant shows that under visible light irradiation the first order rate constant of degradation catalyzed by alga-based CDs-Cu-TiO₂ reaches 6.4 times of that degraded by pure TiO₂ nanoparticles, and the degradation efficiency after 150 min is close to 100%, which is double of the value when TiO₂ nanoparticles apply.

Key words: CDs-Cu-TiO₂, composite photocatalyst, photocatalytic degradation, dye wastewater

中图分类号:

TQ174

刘彩, 刘芳, 黄方, 王晓娟. 海藻基CDs-Cu-TiO₂复合材料的制备及其光催化性能[J]. 无机材料学报, 2021, 36(11): 1154-1162.

LIU Cai, LIU Fang, HUANG Fang, WANG Xiaojuan. Preparation and Photocatalytic Properties of Alga-based CDs-Cu-TiO₂ Composite Material[J]. Journal of Inorganic Materials, 2021, 36(11): 1154-1162.

图/表 9

图1 CDs-Cu-TiO2复合材料的制备流程图

Fig. 1 Schematic diagram for synthesizing CDs-Cu-TiO2 nanocomposite

图2 TiO2、CDs-TiO2和CDs-Cu-TiO2样品的XRD图谱

Fig. 2 XRD patterns of TiO2, CDs-TiO2 and CDs-Cu-TiO2 composite

图3 样品(A)TiO2, (B)CDs, (C, D)CDs-Cu-TiO2的TEM照片; (E)CDs-Cu-TiO2的SAED图片; (F)CDs-TiO2和CDs-Cu-TiO2样品的EDS分析

Fig. 3 TEM images of (A) TiO2 , (B) CDs, (C, D) CDs-Cu-TiO2; (E) SAED image of CDs-Cu-TiO2 composite; (F) EDS patterns of CDs-TiO2 and CDs-Cu-TiO2 composite

图4 (A)不同样品的XPS全谱图; CDs-Cu-TiO2的(B)C1s, (C)N1s, (D)Cu2p的高分辨分峰拟合谱

Fig. 4 (A) XPS survey spectra of different materials; XPS spectra of (B) C1s, (C) N1s, and (D) Cu2p for the CDs-Cu-TiO2 composite

图5 复合材料的(A)红外光谱和(B)紫外-可见漫反射光谱

Fig. 5 (A)FT-IR spectra and (B) UV-Vis diffuse reflectance spectra of TiO2, CDs-TiO2 and CDs-Cu-TiO2 composite with inset showing the Tauc’s plots

图6 (A)CDs的紫外-可见吸收光谱和荧光发射光谱(激发波长380 nm); (B)不同近红外波长激发的CDs溶液的荧光光谱; (C)TiO2, CDs-TiO2 和 CDs-Cu-TiO2 样品的荧光光谱(激发波长320 nm)

Fig. 6 (A) UV-Vis absorption spectrum and FL spectrum (λex= 380 nm) of CDs; (B) Photoluminescence emission spectra of CDs at different near infrared excitation wavelengths; (C) FL spectra (λex=320 nm) of TiO2, CDs-TiO2 and CDs-Cu-TiO2 composite

图7 (A)不同配比CDs-TiO2催化剂和(B)不同配比CDs-Cu-TiO2催化剂可见光降解RhB; (C)不同催化剂可见光下降解RhB的一级动力学分析; (D)CDs-Cu-TiO2催化降解RhB的循环实验

Fig. 7 RhB degradation under visible light irradiation using CDs-TiO2 (A) or CDs-Cu-TiO2 (B) as the photocatalyst; (C) the first order kinetics of RhB degradation in the presence of various photocatalysts; (D) recycling runs of the photocatalytic activity of CDs-Cu-TiO2 toward RhB degradation

表1 CDs-Cu-TiO2中各元素的原子含量分析

Table 1 Analysis of the atomic content of each element in CDs-Cu-TiO2 composite

Atomic content of each element in CDs-Cu-TiO₂
Element	Ti2p	C1s	N1s	O1s	Cu2p
/%	27.11	13.61	1.14	57.21	0.93

图8 CDs-Cu-TiO2催化剂的光催化机理

Fig. 8 Photocatalytic mechanism of CDs-Cu-TiO2 composite

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海藻基CDs-Cu-TiO₂复合材料的制备及其光催化性能

Preparation and Photocatalytic Properties of Alga-based CDs-Cu-TiO₂ Composite Material

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